Mechanism of Additive-Assisted Room-Temperature Processing of Metal Halide Perovskite Thin Films

Abdelsamie, Maged; Li, Tianyang; Babbe, Finn; Xu, Junwei; Han, Qiwei; Blum, Volker; Sutter-Fella, Carolin M.; Mitzi, David B.; Toney, Michael F.

doi:10.1021/acsami.0c22630

Title: Mechanism of Additive-Assisted Room-Temperature Processing of Metal Halide Perovskite Thin Films

Journal Article · Tue Mar 09 00:00:00 EST 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c22630· OSTI ID:1777974

^[1];

^[2];

^[3]; Xu, Junwei ^[4]; Han, Qiwei ^[2];

^[2];

^[3];

^[2];

^[5]

SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Duke Univ., Durham, NC (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Colorado, Boulder, CO (United States)

Perovskite solar cells have received substantial attention due to their potential for low-cost photovoltaic devices on flexible or rigid substrates. Thiocyanate (SCN)-containing additives, such as MASCN (MA = methylammonium), have been shown to control perovskite film crystallization and the film microstructure to achieve effective room-temperature perovskite absorber processing. Nevertheless, the crystallization pathways and mechanisms of perovskite formation involved in MASCN additive processing are far from clear. Using in situ X-ray diffraction and photoluminescence, we investigate the crystallization pathways of MAPbI₃ and reveal the mechanisms of additive-assisted perovskite formation during spin coating and subsequent N₂ drying. In this work, we confirm that MASCN induces large precursor aggregates in solution and, during spin coating, promotes the formation of the perovskite phase with lower nucleation density and overall larger initial nuclei size, which forms upon reaching supersaturation in solution, in addition to intermediate solvent-complex phases. Finally, during the subsequent N₂ drying, MASCN facilitates the dissociation of these precursor aggregates and the solvate phases, leading to further growth of the perovskite crystals. Our results show that the nature of the intermediate phases and their formation/dissociation kinetics determine the nucleation and growth of the perovskite phase, which subsequently impact the film microstructure. These findings provide mechanistic insights underlying room-temperature, additive-assisted perovskite processing and help guide further development of such facile room-temperature synthesis routes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC36-08G028308; AC02-76SF00515; SC0004993

OSTI ID:: 1777974

Alternate ID(s):: OSTI ID: 1782080

Journal Information:: ACS Applied Materials and Interfaces, Vol. 13, Issue 11; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Thermally Stable MAPbI ₃ Perovskite Solar Cells with Efficiency of 19.19% and Area over 1 cm ² achieved by Additive Engineering Wu, Yongzhen; Xie, Fengxian; Chen, Han Advanced Materials, Vol. 29, Issue 28 https://doi.org/10.1002/adma.201701073	journal	May 2017
Monitoring Thermal Annealing of Perovskite Solar Cells with In Situ Photoluminescence van Franeker, Jacobus J.; Hendriks, Koen H.; Bruijnaers, Bardo J. Advanced Energy Materials, Vol. 7, Issue 7 https://doi.org/10.1002/aenm.201601822	journal	December 2016
Self-formed grain boundary healing layer for highly efficient CH3NH3PbI3 perovskite solar cells Son, Dae-Yong; Lee, Jin-Wook; Choi, Yung Ji Nature Energy, Vol. 1, Issue 7 https://doi.org/10.1038/nenergy.2016.81	journal	June 2016
Toward All Room-Temperature, Solution-Processed, High-Performance Planar Perovskite Solar Cells: A New Scheme of Pyridine-Promoted Perovskite Formation Zhang, Hong; Cheng, Jiaqi; Li, Dan Advanced Materials, Vol. 29, Issue 13 https://doi.org/10.1002/adma.201604695	journal	January 2017
Critical kinetic control of non-stoichiometric intermediate phase transformation for efficient perovskite solar cells Rong, Yaoguang; Venkatesan, Swaminathan; Guo, Rui Nanoscale, Vol. 8, Issue 26 https://doi.org/10.1039/C6NR00488A	journal	January 2016
23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J. Nature Energy, Vol. 2, Issue 4 https://doi.org/10.1038/nenergy.2017.9	journal	February 2017
Recent progress of inorganic perovskite solar cells Tai, Qidong; Tang, Kai-Chi; Yan, Feng Energy & Environmental Science, Vol. 12, Issue 8 https://doi.org/10.1039/C9EE01479A	journal	January 2019
Additive engineering for highly efficient organic–inorganic halide perovskite solar cells: recent advances and perspectives Li, Taotao; Pan, Yufeng; Wang, Ze Journal of Materials Chemistry A, Vol. 5, Issue 25 https://doi.org/10.1039/C7TA01798G	journal	January 2017
The emergence of perovskite solar cells Green, Martin A.; Ho-Baillie, Anita; Snaith, Henry J. Nature Photonics, Vol. 8, Issue 7, p. 506-514 https://doi.org/10.1038/nphoton.2014.134	journal	July 2014
The Impact of Atmosphere on the Local Luminescence Properties of Metal Halide Perovskite Grains Brenes, Roberto; Eames, Christopher; Bulović, Vladimir Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201706208	journal	March 2018
Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides Li, Xiong; Ibrahim Dar, M.; Yi, Chenyi Nature Chemistry, Vol. 7, Issue 9 https://doi.org/10.1038/nchem.2324	journal	August 2015
A Review on Additives for Halide Perovskite Solar Cells Liu, Shuang; Guan, Yanjun; Sheng, Yusong Advanced Energy Materials, Vol. 10, Issue 13 https://doi.org/10.1002/aenm.201902492	journal	April 2020
Interfacial Effects during Rapid Lamination within MAPbI ₃ Thin Films and Solar Cells Dunlap-Shohl, Wiley A.; Li, Tianyang; Mitzi, David B. ACS Applied Energy Materials, Vol. 2, Issue 7 https://doi.org/10.1021/acsaem.9b00747	journal	June 2019
Unreacted PbI ₂ as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells Jacobsson, T. Jesper; Correa-Baena, Juan-Pablo; Halvani Anaraki, Elham Journal of the American Chemical Society, Vol. 138, Issue 32 https://doi.org/10.1021/jacs.6b06320	journal	August 2016
Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3 Stone, Kevin H.; Gold-Parker, Aryeh; Pool, Vanessa L. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05937-4	journal	August 2018
Additive engineering for high-performance room-temperature-processed perovskite absorbers with micron-size grains and microsecond-range carrier lifetimes Han, Qiwei; Bai, Yusong; Liu, Jie Energy & Environmental Science, Vol. 10, Issue 11 https://doi.org/10.1039/C7EE02272G	journal	January 2017
Thermal degradation of CH ₃ NH ₃ PbI ₃ perovskite into NH ₃ and CH ₃ I gases observed by coupled thermogravimetry–mass spectrometry analysis Juarez-Perez, Emilio J.; Hawash, Zafer; Raga, Sonia R. Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE02016J	journal	January 2016
Simple post annealing-free method for fabricating uniform, large grain-sized, and highly crystalline perovskite films Byranvand, Mahdi Malekshahi; Song, Seulki; Pyeon, Limok Nano Energy, Vol. 34 https://doi.org/10.1016/j.nanoen.2017.02.017	journal	April 2017
Additive Enhanced Crystallization of Solution-Processed Perovskite for Highly Efficient Planar-Heterojunction Solar Cells Liang, Po-Wei; Liao, Chien-Yi; Chueh, Chu-Chen Advanced Materials, Vol. 26, Issue 22, p. 3748-3754 https://doi.org/10.1002/adma.201400231	journal	March 2014
Dynamics of Antisolvent Processed Hybrid Metal Halide Perovskites Studied by In Situ Photoluminescence and Its Influence on Optoelectronic Properties Song, Tze-Bin; Yuan, Zhenghao; Babbe, Finn ACS Applied Energy Materials https://doi.org/10.1021/acsaem.9b02052	journal	February 2020
Crystalline Nature of Colloids in Methylammonium Lead Halide Perovskite Precursor Inks Revealed by Cryo-Electron Microscopy Dutta, Nikita S.; Noel, Nakita K.; Arnold, Craig B. The Journal of Physical Chemistry Letters, Vol. 11, Issue 15 https://doi.org/10.1021/acs.jpclett.0c01975	journal	July 2020
Room Temperature Phase Transition in Methylammonium Lead Iodide Perovskite Thin Films Induced by Hydrohalic Acid Additives Soe, Chan Myae Myae; Stoumpos, Constantinos C.; Harutyunyan, Boris ChemSusChem, Vol. 9, Issue 18, p. 2656-2665 https://doi.org/10.1002/cssc.201600879	journal	September 2016
High efficiency methylammonium lead triiodide perovskite solar cells: the relevance of non-stoichiometric precursors Roldán-Carmona, C.; Gratia, P.; Zimmermann, I. Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE02555A	journal	January 2015
Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation Abdelsamie, Maged; Xu, Junwei; Bruening, Karsten Advanced Functional Materials, Vol. 30, Issue 38 https://doi.org/10.1002/adfm.202001752	journal	July 2020
Triple-cation mixed-halide perovskites: towards efficient, annealing-free and air-stable solar cells enabled by Pb(SCN)2 additive Sun, Yong; Peng, Jiajun; Chen, Yani Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep46193	journal	April 2017
Confining metal-halide perovskites in nanoporous thin films Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko Science Advances, Vol. 3, Issue 8 https://doi.org/10.1126/sciadv.1700738	journal	August 2017
Monolithic all-perovskite tandem solar cells with 24.8% efficiency exploiting comproportionation to suppress Sn(ii) oxidation in precursor ink Lin, Renxing; Xiao, Ke; Qin, Zhengyuan Nature Energy, Vol. 4, Issue 10 https://doi.org/10.1038/s41560-019-0466-3	journal	September 2019
Photovoltaic solar cell technologies: analysing the state of the art Nayak, Pabitra K.; Mahesh, Suhas; Snaith, Henry J. Nature Reviews Materials, Vol. 4, Issue 4 https://doi.org/10.1038/s41578-019-0097-0	journal	March 2019
Low-dimensional perovskite nanoplatelet synthesis using in situ photophysical monitoring to establish controlled growth Do, Mai; Kim, Irene; Kolaczkowski, Matthew A. Nanoscale, Vol. 11, Issue 37 https://doi.org/10.1039/C9NR04010B	journal	January 2019
Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells Ke, Weijun; Xiao, Chuanxiao; Wang, Changlei Advanced Materials, Vol. 28, Issue 26 https://doi.org/10.1002/adma.201600594	journal	May 2016
Room-Temperature Formation of Highly Crystalline Multication Perovskites for Efficient, Low-Cost Solar Cells Matsui, Taisuke; Seo, Ji-Youn; Saliba, Michael Advanced Materials, Vol. 29, Issue 15 https://doi.org/10.1002/adma.201606258	journal	January 2017
Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms10030	journal	November 2015
Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases Munir, Rahim; Sheikh, Arif D.; Abdelsamie, Maged Advanced Materials, Vol. 29, Issue 2 https://doi.org/10.1002/adma.201604113	journal	November 2016
Bulk heterojunction perovskite hybrid solar cells with large fill factor Wang, Kai; Liu, Chang; Du, Pengcheng Energy & Environmental Science, Vol. 8, Issue 4 https://doi.org/10.1039/C5EE00222B	journal	January 2015
Identifying the Molecular Structures of Intermediates for Optimizing the Fabrication of High-Quality Perovskite Films Cao, Jing; Jing, Xiaojing; Yan, Juanzhu Journal of the American Chemical Society, Vol. 138, Issue 31 https://doi.org/10.1021/jacs.6b04924	journal	August 2016
Extending the Photovoltaic Response of Perovskite Solar Cells into the Near‐Infrared with a Narrow‐Bandgap Organic Semiconductor Zhao, Xiaoming; Yao, Chao; Liu, Tianran Advanced Materials, Vol. 31, Issue 49 https://doi.org/10.1002/adma.201904494	journal	September 2019
Thermal engineering of FAPbI3 perovskite material via radiative thermal annealing and in situ XRD Pool, Vanessa L.; Dou, Benjia; Van Campen, Douglas G. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14075	journal	January 2017
Chemical Pathways Connecting Lead(II) Iodide and Perovskite via Polymeric Plumbate(II) Fiber Guo, Yunlong; Shoyama, Kazutaka; Sato, Wataru Journal of the American Chemical Society, Vol. 137, Issue 50 https://doi.org/10.1021/jacs.5b10599	journal	December 2015
Potassium- and Rubidium-Passivated Alloyed Perovskite Films: Optoelectronic Properties and Moisture Stability Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Pearson, Andrew J. ACS Energy Letters, Vol. 3, Issue 11 https://doi.org/10.1021/acsenergylett.8b01504	journal	September 2018
Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics Oosterhout, Stefan D.; Savikhin, Victoria; Zhang, Junxiang Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00067	journal	March 2017
Enabling Flexible All-Perovskite Tandem Solar Cells Palmstrom, Axel F.; Eperon, Giles E.; Leijtens, Tomas Joule, Vol. 3, Issue 9 https://doi.org/10.1016/j.joule.2019.05.009	journal	September 2019
Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes Song, Tze‐Bin; Yuan, Zhenghao; Mori, Megumi Advanced Functional Materials, Vol. 30, Issue 6 https://doi.org/10.1002/adfm.201908337	journal	December 2019
Crystal Structure of DMF-Intermediate Phases Uncovers the Link Between CH ₃ NH ₃ PbI ₃ Morphology and Precursor Stoichiometry Petrov, Andrey A.; Sokolova, Iuliia P.; Belich, Nikolai A. The Journal of Physical Chemistry C, Vol. 121, Issue 38 https://doi.org/10.1021/acs.jpcc.7b08468	journal	September 2017
Recent progress towards roll-to-roll manufacturing of perovskite solar cells using slot-die processing Li, Hengyue; Zuo, Chuantian; Scully, Andrew D. Flexible and Printed Electronics, Vol. 5, Issue 1 https://doi.org/10.1088/2058-8585/ab639e	journal	January 2020
Control of Crystal Growth toward Scalable Fabrication of Perovskite Solar Cells Lee, Jin‐Wook; Lee, Do‐Kyoung; Jeong, Dong‐Nyuk Advanced Functional Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adfm.201807047	journal	December 2018
Low-temperature-processed efficient semi-transparent planar perovskite solar cells for bifacial and tandem applications Fu, Fan; Feurer, Thomas; Jäger, Timo Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9932	journal	November 2015
Retarding the crystallization of PbI ₂ for highly reproducible planar-structured perovskite solar cells via sequential deposition Wu, Yongzhen; Islam, Ashraful; Yang, Xudong Energy Environ. Sci., Vol. 7, Issue 9 https://doi.org/10.1039/C4EE01624F	journal	January 2014
Optical in situ monitoring during the synthesis of halide perovskite solar cells reveals formation kinetics and evolution of optoelectronic properties Suchan, Klara; Just, Justus; Becker, Pascal Journal of Materials Chemistry A, Vol. 8, Issue 20 https://doi.org/10.1039/D0TA01237H	journal	January 2020
A polymer scaffold for self-healing perovskite solar cells Zhao, Yicheng; Wei, Jing; Li, Heng Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10228	journal	January 2016
Get the Basics Right: Jacobian Conversion of Wavelength and Energy Scales for Quantitative Analysis of Emission Spectra Mooney, Jonathan; Kambhampati, Patanjali The Journal of Physical Chemistry Letters, Vol. 4, Issue 19 https://doi.org/10.1021/jz401508t	journal	October 2013
Intermixing-seeded growth for high-performance planar heterojunction perovskite solar cells assisted by precursor-capped nanoparticles Li, Shao-Sian; Chang, Chi-Huang; Wang, Ying-Chiao Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE03229F	journal	January 2016
Understanding how excess lead iodide precursor improves halide perovskite solar cell performance Park, Byung-wook; Kedem, Nir; Kulbak, Michael Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05583-w	journal	August 2018
Enabling room-temperature processed highly efficient and stable 2D Ruddlesden–Popper perovskite solar cells with eliminated hysteresis by synergistic exploitation of additives and solvents Yu, Shuang; Yan, Yajie; Chen, Yani Journal of Materials Chemistry A, Vol. 7, Issue 5 https://doi.org/10.1039/C8TA09146C	journal	January 2019
The Second Spacer Cation Assisted Growth of a 2D Perovskite Film with Oriented Large Grain for Highly Efficient and Stable Solar Cells Lian, Xiaomei; Chen, Jiehuan; Qin, Minchao Angewandte Chemie, Vol. 131, Issue 28 https://doi.org/10.1002/ange.201902959	journal	May 2019
Perovskite/polymer monolithic hybrid tandem solar cells utilizing a low-temperature, full solution process Chen, Chun-Chao; Bae, Sang-Hoon; Chang, Wei-Hsuan Materials Horizons, Vol. 2, Issue 2 https://doi.org/10.1039/C4MH00237G	journal	January 2015
Kinetic Stabilization of the Sol-Gel State in Perovskites Enables Facile Processing of High-Efficiency Solar Cells Wang, Kai; Tang, Ming-Chun; Dang, Hoang X. Advanced Materials, Vol. 31, Issue 32 https://doi.org/10.1002/adma.201808357	journal	June 2019
Room temperature formation of organic–inorganic lead halide perovskites: design of nanostructured and highly reactive intermediates Zhang, Hong; Li, Dan; Cheng, Jiaqi Journal of Materials Chemistry A, Vol. 5, Issue 7 https://doi.org/10.1039/C6TA09845B	journal	January 2017
Hybrid Organic-Inorganic Perovskites (HOIPs): Opportunities and Challenges Berry, Joseph; Buonassisi, Tonio; Egger, David A. Advanced Materials, Vol. 27, Issue 35 https://doi.org/10.1002/adma.201502294	journal	July 2015
Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques Liu, Dianyi; Kelly, Timothy L. Nature Photonics, Vol. 8, Issue 2, p. 133-138 https://doi.org/10.1038/nphoton.2013.342	journal	December 2013

Similar Records

Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

Journal Article · Mon Dec 09 00:00:00 EST 2019 · Advanced Functional Materials · OSTI ID:1777974

Song, Tze‐Bin; Yuan, Zhenghao; Mori, Megumi; +7 more

Impact of processing conditions on the film formation of lead-free halide double perovskite Cs₂AgBiBr₆

Journal Article · Wed May 18 00:00:00 EDT 2022 · Journal of Materials Chemistry. A · OSTI ID:1777974

Abdelsamie, Maged; Cruse, Kevin; Tamura, Nobumichi; +2 more

Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation

Journal Article · Wed Jul 15 00:00:00 EDT 2020 · Advanced Functional Materials · OSTI ID:1777974

Abdelsamie, Maged; Xu, Junwei; Bruening, Karsten; +3 more

Related Subjects

36 MATERIALS SCIENCE
room-temperature processing
additive engineering
halide perovskites
crystallization dynamics
film formation mechanism
precursor aggregates
in situ GIWAXS
in situ photoluminescence

Title: Mechanism of Additive-Assisted Room-Temperature Processing of Metal Halide Perovskite Thin Films

Citation Formats

References (59)

Similar Records

Related Subjects